TWI690507B - Novel alkylthio acid derivatives and perfume compositions containing the same - Google Patents

Abstract

The present invention provides a novel alkylthio acid derivative, which can impart a characteristic aroma and fragrance to fragrance cosmetics, foods and beverages, and the like; and a fragrance composition containing the compound as an active ingredient.

A 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester, which is represented by the following formula (1); and a fragrance composition, which contains the following formula (1) Shown is 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester as an active ingredient.

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

Description

Novel alkylthio acid derivatives and perfume compositions containing the same

The present invention relates to a novel alkylthio acid derivative useful as a perfume compound, etc., and a perfume composition containing the compound as an active ingredient.

In recent years, consumers' tastes have diversified, and foods and beverages with various aromas have been produced. For example, in the food and beverage industry, in order to cater to the taste of consumers, or to meet the needs of foods and beverages with natural flavors and fragrances, various technical developments are required.

The fragrance, which is one of the raw materials for food and beverage, cannot be adequately matched only with the fragrance compounds proposed in the past, but has unique fragrance and fragrance characteristics that were not available in the past, and not only the fragrance and fragrance characteristics, but also their sustainability. The development of an excellent perfume composition becomes a problem.

In addition, for perfumery and cosmetics, with the diversification of consumer preferences, the development of various perfumery products is also expected. Among fragrances used in fragrance cosmetics, there is a constant demand for materials with novel fragrances. The current situation is that the combination of previous fragrance materials cannot fully meet this demand, and the demand for new fragrance materials is increasing.

So far, several proposals have been made for improving the aroma. For example, Patent Document 1 discloses that cis-6-dodecene-4-lactone containing an optically active substance or a racemate enhances the persistent sweet fermentation of fermented foods and drinks. However, the effect is limited to fermented foods and drinks.

In addition, by including 2-methyl-3-thiophene mercaptan or 3-mercapto-3-methylbutyl formate in foods and beverages, it is possible to enhance the sesame-like freshness, freshness, and greasy feel (Patent Literature 2, 3). However, these compounds can enhance the specific aroma similar to sesame, but it is hard to say that it can obtain good effects compared to the effect of imparting sesame-like aroma when it is commonly used to enhance the general aroma.

In addition, δ-lactones are known as perfume compounds, and Patent Document 4 discloses that δ-lactones enhance the oily feel. However, delta-lactones are known perfume compounds, so it is difficult to impart a unique fragrance that conventional perfume compounds did not have.

Furthermore, Patent Document 5 discloses specific disulfides (for example, furan methyl methyl disulfide, methyl 2-methyl-3-furan disulfide, and difuran methyl disulfide). The soy sauce or soy sauce flavor-imparting agent imparts a soy sauce with a fermentation and ripening feeling. However, it has effects only on specific foods and beverages, and therefore it cannot be used in general foods and beverages or fragrance cosmetics.

Therefore, there is a need to propose fragrance compounds that can provide better effects on aromas, fats, fermentation, thickness, and freshness for fragrance cosmetics and food and beverage products.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2001-112431

Patent Document 2: Japanese Patent No. 4931900

Patent Document 3: Japanese Patent No. 4931901

Patent Document 4: Japanese Patent Laid-Open No. 2011-83264

Patent Literature 5: Japanese Patent No. 6076037

An object of the present invention is to provide a novel alkylthio acid derivative that can impart fragrance and fragrance to fragrance cosmetics and food and beverages, and a fragrance composition containing the compound as an active ingredient.

The inventors of the present application have made a careful study to solve the above-mentioned problems and found that: by making 5-[(1-alkoxy)ethoxy]alkanoic acid alkyl ester into 5-[(1- Alkoxy)ethoxy]alkylthio acid S-alkyl ester (1) has oily, fatty, fermentation, thick, refreshing, onion-like, meat-like aroma characteristics, and the compound itself Or a fragrance composition containing the compound can be added to fragrance cosmetics and food and beverage products to improve or enhance the fragrance and fragrance, and then complete the present invention.

Therefore, this specification discloses the following topics. Themes such as the foregoing are also called revealing matters.

Theme 1: A 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester, which is represented by the following formula (1).

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

Theme 2: A fragrance composition containing 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the following formula (1) as an active ingredient.

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

Theme 3: A composition comprising 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the following formula (1) and a diluent.

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

Theme 4: A fragrance or food or drink, which contains the compound as described in Theme 1.

Theme 5: A fragrance or food or drink, which contains the composition described in Theme 2 or 3.

Theme 6: A 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester, which is represented by the following formula (1), in order to impart fragrance or scent to fragrance cosmetics or food and beverage use.

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

Theme 7: A method for imparting or enhancing the fragrance or scent of a fragrance or food and beverage, which comprises adding an effective amount of the following formula (1) to a fragrance or food or beverage that needs to impart or enhance the fragrance or scent The steps of 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester are shown.

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].

The 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester of the present invention has a characteristic aroma, and when mixed with other perfume compounds, a unique aroma can be added to the perfume composition Characteristics, and to improve or enhance this aroma and fragrance, and by adding a fragrance composition containing 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester to food and beverage, it can be provided Add unique aroma characteristics to the products targeted by it, and have the characteristics of improving or enhancing aroma and fragrance, and cater to consumers' diverse and rich fragrances or foods and beverages.

[Forms for carrying out the invention]

The contents or topics disclosed in this specification will be described in detail below.

Examples of the compound represented by formula (1) or 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester include, for example, 5-[(1-ethoxy)ethoxy Group] Hexanethio acid S-methyl ester, 5-[(1-ethoxy)ethoxy]octane thio acid S-methyl ester, 5-[(1-ethoxy)ethoxy] Decane thioacid S-methyl ester, 5-[(1-ethoxy)ethoxy]octane thioacid S-methyl ester, 5-[(1-ethoxy)ethoxy] twelve Alkyl thioacid S-methyl ester, 5-[(1-ethoxy)ethoxy]tetradecane thioacid S-methyl ester, 5-[(1-propoxy)ethoxy]tetradecane Alkyl thioacid S-methyl ester, 5-[(1-butoxy)ethoxy]decane thioacid S-methyl ester, 5-[(1-butoxy)ethoxy]tetradecane Thio acid S-methyl ester, 5-[(1-ethoxy)ethoxy]decane thio acid S-ethyl ester, 5-[(1-ethoxy)ethoxy]tetradecane sulfur Substituted acid S-ethyl ester, 5-[(1-butoxy)ethoxy]decane thioacid S-ethyl ester, etc.

Typical compounds include 5-[(1-ethoxy)ethoxy]alkylthio acid S-methyl ester represented by the following formula (2).

[In formula (2), R ₁ represents an alkyl group having 1 to 9 carbons].

As a more typical compound, 5-[(1-ethoxy)ethoxy]decanethio acid S-methyl ester, 5-[(1-ethoxy)ethoxy]tetradecane The thioacid S-methyl ester is preferably a typical compound as described above as a fragrance compound, but it is not limited thereto.

The 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the formula (1) can be produced according to the reaction pathway shown in the following reaction scheme 1 and reaction scheme 2, for example .

[In Formula (3) to Formula (5), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₄ represents a methyl group or an ethyl group].

In the first step of the above reaction, a transesterification reaction is applied to delta-lactone, and the intramolecular ester bond undergoes a ring-opening reaction to obtain a hydroxy ester. Examples include the method of reacting with methanol or ethanol.

Furthermore, in the second step of the above reaction, an acetalization reaction can be applied to the hydroxyl group of the hydroxy ester obtained in the first step. For example, a method of performing an exchange reaction with acetaldehyde dialkyl acetal in the presence of an acid catalyst, and a method of more simply reacting with an alkyl vinyl ether in the presence of an acid catalyst.

[In formula (5) to formula (6), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, R ₃ represents a methyl group or an ethyl group, and R ₄ represents a methyl group Or ethyl, R ₅ represents an alkyl group having 1 to 6 carbons].

In addition, the third step of the above reaction is to make the 5-[(1-alkoxy)ethoxy]alkanoic acid alkyl ester obtained in the second step, in the presence or absence of a base and an alcohol, to carry out the base The resulting carboxylate reacts with the halogenated amide to give 5-[(1-alkoxy)ethoxy]alkanoic anhydride. For example, it can be obtained by reacting potassium carboxylate salt obtained in the presence of potassium hydroxide and ethanol with acetyl chloride.

Furthermore, the fourth step of the above reaction is to obtain 5-[(1-alkoxy)ethoxy]alkylsulfide, which is one of the matters disclosed in this specification, by reaction with the sodium salt of alkylthiol S-alkyl esters.

The following describes the details for each step, but it is not intended to limit the subject matter or disclosure of this specification to such content.

The delta-lactone of the formula (3) used as the starting material of the first step can be any one synthesized by a general method or a commercially available product. Examples of commercially available products include δ-caprolactone (manufactured by Tokyo Chemical Industry Co., Ltd.), δ-octanolactone (manufactured by Tokyo Chemical Industry Co., Ltd.), δ-nonanolide (manufactured by Sigma-Aldrich), and δ-decane Lactone (manufactured by Tokyo Chemical Industry Co., Ltd.), δ-undecalactone (manufactured by Sigma-Aldrich), δ-dodecanolide (manufactured by Sigma-Aldrich), δ-tridecanolide (manufactured by Tokyo Chemical Industry) ), delta-tetradecanolide (manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

By reacting with sodium alkoxide in an alcohol solvent, the alkyl 5-hydroxyalkanoate represented by formula (4) can be produced.

As the alcohol used, methanol or ethanol is used, and the amount of use per mol of delta-lactone is usually 1.0 to 200.0 mol, preferably 30.0 to 80.0 mol.

This reaction is usually carried out at a temperature in the range of 70°C to 90°C, preferably 75°C to 85°C, usually for 30 minutes to 24 hours, preferably for about 30 minutes to 12 hours.

The crude product containing the obtained compound (4) is neutralized with an alkaline substance, extracted by a reaction solvent and other general post-treatment methods, and the obtained 5-hydroxyalkanoic acid alkyl ester represented by the formula (4) is obtained. Used directly in the next step.

In the next second step, the 5-hydroxyalkanoic acid alkyl ester represented by formula (4) can be used in an aprotic solvent to react it with alkyl vinyl ether to produce the formula (5). Shown is 5-[(1-alkoxy)ethoxy]alkyl alkanoate.

The alkyl vinyl ether used in the second step may be any one synthesized by a general method or a commercially available product. Examples of commercially available products include ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), propyl vinyl ether (manufactured by Sigma-Aldrich), butyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

The alkyl vinyl ether, per 1-mole alkyl 5-hydroxyalkanoate, can generally be used in the range of 1.0 to 5.0 mol, preferably 1.5 to 3.5 mol. The reaction method is preferably a method of adding alkyl vinyl ether dropwise. The dropwise addition of alkyl vinyl ether to ethyl 5-hydroxyalkanoate is in the range of 0°C to 20°C, preferably 0°C to 15°C. The internal temperature is usually 5 minutes to 45 minutes, preferably about 10 minutes to 30 minutes. The reaction time is not particularly limited, but after the alkyl vinyl ether dropping is completed, a reaction of more than 1 hour is required.

The solvent used is not particularly limited as long as it is an aprotic solvent, and hydrocarbon solvents such as hexane and toluene, ether solvents such as diethyl ether and tetrahydrofuran can be used. The reaction is performed by adding an acid catalyst, and examples of the acid catalyst used include mineral acids such as benzenesulfonic acid, p-toluenesulfonic acid, and pyridine salts thereof, concentrated sulfuric acid, and phosphoric acid. Preferable examples include pyridinium p-toluenesulfonate.

The crude product containing the obtained compound represented by the formula (5) can be washed with an alkaline aqueous solution, the reaction solvent can be recovered, and the 5-[(1-alkoxy)ethoxy]alkanoic acid ester can be isolated. The obtained compound of formula (5) can be purified by means such as column chromatography or reduced-pressure distillation, if necessary.

In the next third step, after adding potassium hydroxide and ethanol to the compound represented by formula (5), the carboxylic acid salt obtained by alkalization is reacted with the halide to obtain 5-[represented by formula (6)] (1-alkoxy)ethoxy]alkanoic anhydride. Examples of the halogenated amides include benzoyl chloride, 2,4,6-trichlorobenzoyl chloride, and trimethyl acetyl chloride. Preferably, benzoyl chloride or trimethyl acetyl chloride can be exemplified.

The halogen halide used in the third step may be any one synthesized by a general method or a commercially available product. Examples of commercially available products include benzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and trimethyl acetyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.).

The halides are 5-((1-alkoxy)ethoxy]alkyl alkanoates per 1 mole, usually in the range of 0.5 to 3.0 moles, preferably in the range of 0.5 to 2.0 moles. The reaction method is preferably a method of adding dropwise halides to the carboxylate. The dropwise addition is a temperature in the range of 0°C to 20°C, preferably 0°C to 15°C, usually 5 minutes to 45 minutes 3. Preferably, the dropping is performed in about 10 minutes to 35 minutes.

In the next fourth step, the compound represented by formula (6) is reacted with the sodium salt of alkylthiol to obtain 5-[(1-alkoxy)ethoxy]alkylthio represented by formula (1) Acid S-alkyl ester. Alkyl mercaptan sodium salt includes methyl mercaptan sodium salt and ethyl mercaptan sodium salt.

The sodium salt of the alkylthiol used in the fourth step may be any one synthesized by a general method or a commercially available product. Examples of commercially available products include methyl mercaptan sodium salt (manufactured by Tokyo Chemical Industry Co., Ltd.) and ethyl mercaptan sodium salt (manufactured by Sigma-Aldrich).

The fourth step is preferably a method of adding the reaction droplet obtained in the third step to the sodium salt of alkylthiol added in advance, at a temperature in the range of 5°C to 25°C, preferably 10°C to 20°C , Usually from 5 minutes to 45 minutes, preferably from 10 minutes to 35 minutes or so. The reaction time is not particularly limited, but after the completion of the dropwise addition of the reaction solution, a reaction of more than 1 hour is required. The end point of the reaction is preferably judged by GLC analysis.

The compound represented by the formula (1) obtained by the aforementioned reaction can be purified by a usual purification method, for example, it can be purified by distillation or silica gel column chromatography.

In the present specification, "fragrance" (or aroma) is used in addition to the fragrance received from the nasal cavity, including refreshing feeling, burning feeling, tingling feeling, and the like. On the other hand, "fragrance" (or flavor) is a term similar to "fragrance", but generally speaking, when included in food, the nose, mouth, tongue, throat, etc. bear the aroma, taste, touch The physical, chemical, and functional factors such as sensation are used separately from aroma. In addition, in this specification, "fragrant cosmetics" are abbreviations for scented products and cosmetics, and are used to mean fragrances other than food fragrances.

The 5-[(1-alkoxy)ethoxy]alkyl thioacid S-alkyl ester shown in formula (1) is used for oily, fatty, fermented, thick, fresh, and similar onions , Similar to the aroma of meat, it can be directly blended into perfumery or food and beverage, which can give or enhance the characteristic aroma and fragrance, but can also be mixed with other ingredients as needed to contain water, ethanol, propylene glycol, plants The composition of thinner such as oil is used to prepare citrus, fruit, mint, spice, nut, meat, milk, aquatic product, vegetable, tea, coffee, vanilla, etc. A spice composition, a spice composition for scented cosmetics with citrus notes, fruity notes, woody notes, etc., and using the spice composition to impart or enhance the fragrance‧scent to a cosmetic or food or drink product

Furthermore, the 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the formula (1) may be used by mixing two or more of these in an arbitrary ratio, and, It can also be used by mixing with other perfume ingredients. Examples of other perfume components that can be included with the 5-[(1-alkoxy)ethoxy]alkylthioacid S-alkyl ester include "Japanese Patent Office, Well-known Conventional Technology Collection (Fragrance) Part II Food Fragrances, pages 7-87, issued on January 14, 2012" and "Japan Patent Office, Well-known Technology Collection (Fragrants) Part III Fragrance Cosmetics Fragrances, pages 49-103, June 15, 2013 Synthetic fragrances, natural essential oils, natural fragrances, animal and plant extracts, etc. as described in "Daily Issue".

、甲基吡

、香葉腈等含氮化合物類；甲硫醇、異丁基硫醇、2,4-二甲硫基甲烷、二甲硫醚、二甲基二硫醚、二甲基三硫醚、二甲基亞碸、二甲碸、甲基磺醯基甲烷、異硫氰酸甲酯、異硫氰酸乙酯、異硫氰酸烯丙酯、2-甲基-3-丁硫醇、甲硫基丙醛(methional)、硫代乙酸乙酯、硫代丁酸甲酯、異硫氰酸3-丁烯酯、2-甲基噻吩、苯并噻唑、硫噻唑(sulfurol)、乙醯基硫代乳酸甲酯、丙醯基硫代乳酸甲酯、丁醯基硫代乳酸甲酯、戊醯基硫代乳酸甲酯、2-甲基丁醯基硫代乳酸甲酯、癸醯基硫代乳酸甲酯、乙醯基硫代乳酸乙酯、丙醯基硫代乳酸乙酯、 丁醯基硫代乳酸乙酯、戊醯基硫代乳酸乙酯、異己醯基硫代乳酸丙酯等之含硫化合物類等周知香料化合物；甜橙(orange)、檸檬、佛手柑、紅橘(mandarin)、薄荷、綠薄荷、薰衣草、風信子、洋甘菊、迷迭香、桉樹、鼠尾草、羅勒、玫瑰、格蓬、天竺葵、茉莉、伊蘭花、大茴香、丁香、薑、肉豆蔻、豆蔻、雪松、扁柏、香根草、廣藿香、勞丹脂等天然萃取物‧天然精油。 Examples include hydrocarbons such as myrcene, camphene, limonene, terpinolene, cedarene, caryophyllene, longleane, 1,3,5-undectriene; ethanol, propanol, butanol, Amyl alcohol, isoprenol, hexanol, (Z)-3-hexene-1-ol, heptanol, octanol, 1-octen-3-ol, nonanol, 2,6-nonadiene Alcohol, decanol, dodecanol, linalool, geraniol, nerol, citronellol, dihydromyrcenol, menthol, terpineol, farnesol, nerol tertiary alcohol, Sandalwood alcohol, cedar alcohol, benzyl alcohol, cinnamyl alcohol, phenyl ethanol, furan methanol, acetyl methyl methanol, dimethyl benzyl methanol and other alcohols; acetaldehyde, propionaldehyde, butyraldehyde, 2-butene Aldehyde, hexanal, (E)-2-hexenal, octanal, 4-heptenal, 2,4-octadienal, nonanal, 2-nonenal, 2,4-nonadienal , 2,6-nonadienal, decanal, 2,4-decadienal, undecanal, 10-undecenal, 2,4-undecadienal, dodecanal, citronella Aldehydes such as aldehyde, citral, hydroxycitronellal, benzaldehyde, cinnamaldehyde, α-pentylcinnamaldehyde, phenylacetaldehyde, vanillin, ethyl vanillin, furan formaldehyde, piperonal; 2-heptanone, 2-octanone, 3-octanone, 1-octen-3-one, 2-nonanone, 3-nonanone, 8-nonen-2-one, 2-undecone, 2-tridecone, Acetylmethylmethanol, 5-hydroxy-4-octanone, diacetyl, 2,3-pentanedione, 2,3-hexanedione, 2,3-heptanedione, carvone, menthone, Nocardone, dihydrojasmone, α-ionone, β-ionone, methyl ionone, α-damascone, β-damascenone, β-damascenone, acetocedarene , Raspberry ketone, p-methoxyacetophenone, benzophenone, maltol, ethyl maltol, cyclotene, 2,5-dimethyl-4-hydroxy-3 ( 2H)-furanone and other ketones; ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, decyl acetate, dodecyl acetate, agarwood acetate, geranyl acetate, menthyl acetate, dihydrogen Methyl jasmonate, phenethyl acetate, ethyl lactate, ethyl butyrate, ethyl 2-methylbutanoate, ethyl 3-ethylbutanoate, methyl valerate, methyl caproate, caproic acid Ethyl ester, methyl heptanoate, ethyl heptanoate, ethyl octoate, isoamyl octoate, heptyl octoate, methyl nonanoate, ethyl nonanoate, methyl caprate, ethyl caprate, ethyl undecanoate Ester, methyl laurate, ethyl laurate, ethyl myristate, ethyl palmitate, methyl salicylate, diethyl succinate, diethyl sebacate, ethyl 5-hydroxyhexanoate, Ethyl 5-hydroxydecanoate, ethyl 5-hydroxyundecanoate, propyl 5-hydroxydecanoate, isopropyl 5-hydroxydecanoate, 2-methylpropyl 5-hydroxyoctanoate, 5-hydroxy-9 -Ethyl methyldecanoate, methyl 5-acetoxydecanoate, ethyl 5-acetoxydecanoate, benzyl acetate, benzyl propionate and other esters; from γ-caprolactone , Γ-heptanolide, γ-octanolactone, γ-nonalactone, γ-decalactone, 7-decene-4-lactone, 3-methyl 4-decene-4-lactone, 3-methyl-5-decene-4-lactone, γ-undecalactone, γ-dodecanolide, γ-tridecanolide, γ- Myristyl lactone, δ-caprolactone, 2-hexene-5-lactone, 2-heptene-5-lactone, δ-octanolactone, 2-octene-5-lactone, 4-methyl Yl-5-octanolactone, delta-nonalactone, 2-nonene-5-lactone, 4-methyl-5-nonolactone, delta-decalactone, 2-decene-5-lactone , 4-methyl-5-decalactone, δ-undecalactone, 2-undecene-5-lactone, 4-methyl-5-undecalactone, δ-dodecanolide, 2 -Dodecene-5-lactone, 4-methyl-5-dodecanolide, delta-tridecanolide, 2-tridecene-5-lactone, 4-methyl-5-tridecanolide Esters, delta-tetradecanolide, 2-tetradecene-5-lactone, 2-pentadecen-5-lactone, 2-hexadecene-5-lactone, 2-heptadecene-5- Lactone, 2-octadecene-5-lactone, 2-nonadecene-5-lactone, 2-eicosene-5-lactone, ε-decalactone, cyclopentadecanolactone Lactones such as macrocyclic lactones; ethers such as rose oxide, cedryl methyl ether, oxidized linalool, mint furan, theaspirane; propionic acid, Butyric acid, 2-methylbutyric acid, valeric acid, isovaleric acid, hexanoic acid, trans-2-hexenoic acid, heptanoic acid, octanoic acid, nonanoic acid, 5-hydroxynonanoic acid, capric acid, 2-decene Acid, 4-decenoic acid, 5-decenoic acid, 6-decenoic acid, 9-decenoic acid, 5-hydroxydecanoic acid, 5-hydroxyundecanoic acid, lauric acid, 5-hydroxydodecanoic acid, meat Fatty acids such as myristic acid, pentadecanoic acid, isopentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, linoleic acid, hypolinolenic acid; eugenol, isoeugenol, 4-ethylheal Phenols such as trophol; methyl anthranilate, trimethylamine, indole, skatole, pyridine, isoquinoline, pyridine

Methylpyridine

, Nitrogen compounds such as geraniol; methyl mercaptan, isobutyl mercaptan, 2,4-dimethylthiomethane, dimethyl sulfide, dimethyl disulfide, dimethyl trisulfide, di Methyl sulfoxide, dimethyl sulfoxide, methyl sulfonyl methane, methyl isothiocyanate, ethyl isothiocyanate, allyl isothiocyanate, 2-methyl-3-butanethiol, methyl alcohol Thiopropionaldehyde (methional), ethyl thioacetate, methyl thiobutyrate, 3-butenyl isothiocyanate, 2-methylthiophene, benzothiazole, sulfurol, acetoyl Methyl thiolactate, Methyl propyl thio lactic lactate, Methyl butyl thio lactic lactate, Methyl pentyl thio lactic lactate, Methyl 2-methyl butyl thio lactic lactate, Methyl decyl thio lactic lactate , Sulfur-containing compounds such as ethyl acetoyl thiolactic acid ethyl ester, propyl acetyl thiolactic acid ethyl ester, butyl acetyl thiolactic acid ethyl ester, pentyl acetyl thiolactic acid ethyl ester, isopropyl acetoyl thiolactic acid propyl ester, etc. Well-known spice compounds; orange, lemon, bergamot, mandarin, mint, spearmint, lavender, hyacinth, chamomile, rosemary, eucalyptus, sage, basil, rose, gerber, Natural extracts such as geranium, jasmine, ylang-ylang, fennel, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, labdanum and other natural essential oils.

Fragrance composition containing 5-[(1-alkoxy)ethoxy]alkyl thioacid S-alkyl ester, if necessary, may be contained in the fragrance composition commonly used as the aforementioned diluent or fragrance retention agent solvent Functional water, ethanol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, glycerin, hexanediol, benzyl benzoate, triethyl citrate, diethyl phthalate Ester, methyl rosinate, fatty acid triglyceride, fatty acid diglyceride, etc.

5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester has its own characteristic aroma, but due to the change with time, it will generate a strong sense of fat, similar to cabbage, Alkyl mercaptans (especially methyl mercaptan and ethyl mercaptan) like aromas of onion and garlic, etc., and therefore also have uses as precursors of alkyl mercaptans.

5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester, as described above, it is used alone, or prepared containing 5-[(1-alkoxy)ethoxy ] The fragrance composition of alkylthio acid S-alkyl ester, which imparts the above-mentioned aroma characteristics to cosmetics or foods and beverages, and at the same time can improve or enhance the sense of fat, fat, fermentation, thickness of foods and beverages, Freshness, onion-like aroma, and meat-like aroma.

hai)、雞尾酒飲料、發泡酒、果實酒、草藥酒等酒精飲料類；奶油、乾酪、鮮奶、優格等乳製品；冰淇淋、低乳冰(lact ice)、雪酪、優格、布丁、果凍、日常甜點等甜點類及用以製造此等之混合物類；牛奶糖、糖果、錠型糖果、脆餅乾(cracker)、比司吉(biscuit)、餅乾(cookie)、派、巧克力、零食等糕點類及用以製造此等之蛋糕預拌粉等預拌粉類；麵包、湯、各種速食食品等一般食品類，但並沒有限定於此。 Specific examples of foods and beverages that can improve or enhance the aroma and flavor by the flavor composition containing 5-[(1-alkoxy)ethoxy]alkylthioacid S-alkyl ester include, for example: Cola drinks, carbonated drinks containing fruit juice, carbonated drinks containing milk, etc. carbonated drinks; juice drinks, vegetable drinks, sports drinks, honey drinks, soy milk, vitamin supplement drinks, mineral supplement drinks, nutritional drinks, nourishing drinks, lactic acid bacteria Beverages, milk beverages and other refreshing beverages; green tea, black tea, oolong tea, herbal tea, milk tea, fresh milk coffee, coffee beverages and other hobby beverages; shochu cocktail (Ch

hai), cocktail drinks, sparkling wine, fruit wine, herbal wine and other alcoholic beverages; cream, cheese, fresh milk, yogurt and other dairy products; ice cream, low ice (lact ice), snow cheese, yogurt, pudding , Jelly, daily desserts and other desserts and mixtures used to make these; milk candy, candy, lozenge candy, cracker, cracker, biscuit, cookie, pie, chocolate, snacks Cakes and other pre-mixed powders used to make these cake mixes; general foods such as bread, soup, and various fast-food products, but not limited to this.

Specific examples of fragrance cosmetics that can improve or enhance the fragrance by a fragrance composition containing 5-[(1-alkoxy)ethoxy]alkylthioacid S-alkyl ester include, for example, fragrance Products, basic cosmetics, makeup cosmetics, hair cosmetics, sunscreen cosmetics, medicinal cosmetics, hair care products, soaps, body cleaners, kitchen cleaners, bathing agents, detergents, softeners, bleach, sprays, deodorants ‧Fragrance, insect repellent, oral composition, skin external preparation, medicine, etc., but it is not limited to this.

The blending amount of 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester can be exemplified as follows: 0.01% (1.0×10 ² ppm) to 10%( 1.0×10 ⁵ ppm), preferably 0.05% (5.0×10 ² ppm) to 5.0% (5.0×10 ⁴ ppm), more preferably 0.1% (1.0×10 ³ ppm) to 1.0% (1.0× 10 ⁴ ppm).

The blending amount of the fragrance composition of the product to be used varies depending on the purpose or type of object, but 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester can be exemplified Relative to the total amount in the range of 1 ppb to 100 ppm, preferably 2 ppb to 50 ppm, more preferably 10 ppb to 10 ppm. Within these ranges, it has an excellent effect of imparting or enhancing aromas and fragrances with a sense of oil, fat, fermentation, thickness, and freshness to fragrance cosmetics or food and beverage products.

Hereinafter, the disclosed matters or themes of this specification will be more specifically described based on the embodiments. Furthermore, the embodiments do not intend to limit the technical scope of the subject to the description.

[Example]

In the examples, the measurement of the crude reaction product and the refined product was performed using the following analysis equipment.

GC measurement: GC-2014 (made by Shimadzu Corporation) and Chromatopac C-R8A (made by Shimadzu Corporation)

GC column: TC-1 manufactured by GL Sciences (length 30m, inner diameter 0.53mm, liquid layer thickness 1.50 micrometer)

GC/MS measurement: 5973N (manufactured by Agilent)

GC column: TC-1701 manufactured by GL Sciences (length 30m, inner diameter 0.25mm, liquid layer thickness 0.25 micrometer)

NMR measurement: ECX-400A (manufactured by JEOL RESONANCE).

Example 1: Synthesis of 5-hydroxydecanoic acid ethyl ester

In a 10L four-necked flask, add delta-decalactone (made by Tokyo Chemical Industry Co., Ltd., 1500.0g, 0.10mol) and 99% ethanol (3000.0g) and strong acid cation exchange resin (SK1B-H+, 45.0g), and add Stir at 80±5°C for 3 hours, then stir overnight at room temperature. After filtering the resin with filter paper, it was concentrated under reduced pressure. The obtained concentrate was dried under reduced pressure to obtain crude ethyl 5-hydroxydecanoate (1826.5 g, purity 89.1%).

Example 2: Synthesis of 5-[(1-ethoxy)ethoxy]decanoic acid ethyl ester

The crude product of Example 1 and toluene (3650.0 g) were added to a 10-L four-necked flask, and stirred under ice-water cooling. To this, pyridinium p-toluenesulfonate (44.3 g, 0.2 mol) was added, and ethyl vinyl ether (1270.1 g, 17.6 mol) was added dropwise at 5°C to 10°C for 1 hour. Stir at the same temperature for 1 hour and at room temperature overnight. This was poured into a saturated sodium carbonate aqueous solution (4.4 kg), and after liquid separation, the obtained organic layer was washed with 5% saline, and anhydrous magnesium sulfate powder was added to the organic layer to be dried and concentrated under reduced pressure. The obtained concentrate (2738.0 g) was subjected to precision distillation to obtain ethyl 5-[(1-ethoxy)ethoxy]decanoate (1385.1 g) (yield 2 step 54.5%).

Example 3: Synthesis of 5-[(1-ethoxy)ethoxy]decane thioacid S-methyl ester

Potassium hydroxide (70.1 g, 1.3 mol) and 95% ethanol (1380.0 g) were added to a 3L four-necked flask, and stirred at room temperature. Here, ethyl 5-[(1-ethoxy)ethoxy]decanoate (300.0 g, 1.1 mol) was added and stirred at the same temperature overnight. The reaction liquid was concentrated under reduced pressure to obtain a crude purified product (345.9 g) as a yellow solid.

The crude product (345.9 g), ether (3000 mL) and triethylamine (105.2 g, 1.1 mol) obtained in the previous step were added to a 5L four-necked flask, and stirred under ice-water cooling. Here, trimethyl acetyl chloride (150.7g, 1.3mol) was added dropwise at 5°C to 10°C/30 minutes. Stir for 30 minutes under ice water cooling, and 7 hours at room temperature. The obtained reaction liquid was directly supplied to the next step.

A 10 L four-necked flask was charged with 15% methylmercaptan sodium salt aqueous solution (878.5 g, 1.9 mol), and stirred under ice-water cooling. Here, the reaction liquid obtained in the previous step was added dropwise at 10°C to 20°C/30 minutes, and after the addition was completed, the mixture was stirred at room temperature overnight. The reaction solution was separated, and the aqueous layer was extracted with ether (500 mL). The organic layer was mixed, washed with saturated sodium bicarbonate aqueous solution (1500 mL) and saturated saline aqueous solution (1500 mL) in this order, and dried over anhydrous sodium sulfate. Concentration under reduced pressure and distillation of the obtained crude product (275.6g) to obtain 5-[(1-ethoxy)ethoxy]decane thioacid S-methyl ester (present product 1: 190.5g ) (Yield 3 steps 63.1%).

5-[(1-ethoxy)ethoxy]decane thio acid S-methyl ester

¹ H-NMR (400MHz, C ₆ D ₆ ): δppm 4.64-4.59 (m, 1H), 3.48-3.35 (m, 3H), 2.41 (t, 1H, J=7.4Hz), 2.33 (t, 1H, J=7.4Hz), 1.99(s, 3H), 1.86-1.62(m, 2H), 1.55-1.34(m, 5H), 1.32-1.20(m, 8H), 1.13(q, 3H, J=6.5Hz ), 0.91-0.87(m,3H)

¹³ C-NMR (100 MHz, C ₆ D ₆ ): δ ppm 198.36, 198.27, 98.87, 98.73, 75.69, 75.51, 59.83, 59.67, 44.09, 44.07, 35.03, 34.38, 34.17, 33.48, 32.44, 32.42, 25.44, 25.07, 23.05, 23.01, 21.99, 21.53, 20.75, 15.68, 15.64, 14.29, 14.26, 11.18

Example 4: Synthesis of ethyl 5-hydroxytetradecanoate

In a 200mL four-necked flask, add delta-tetradecanolide (made by Tokyo Chemical Industry Co., Ltd., 45.3g, 0.20mol) and 99% ethanol (90.6g) and strong acid cation exchange resin (SK1B-H+, 1g), and add Stir at 80±5°C for 5 hours, then stir at room temperature overnight. After stirring at room temperature overnight, the filtration resin was filtered with filter paper and concentrated under reduced pressure to obtain crude ethyl 5-hydroxytetradecanoate (60.7 g).

Example 5: Synthesis of ethyl 5-[(1-ethoxy)ethoxy]tetradecanoate

A 200 mL four-necked flask was charged with crude (60.7 g) of Example 4 and toluene (30.0 g), and stirred under ice-water cooling. To this, pyridinium p-toluenesulfonate (1.0 g, 4.0 mmol) was added, and ethyl vinyl ether (22.8 g, 0.40 mol) was added dropwise at 3°C/10 minutes. After stirring under ice water cooling for 2.5 hours, it was stirred at room temperature for 1 hour. After pouring into a saturated sodium carbonate aqueous solution (100 mL), liquid separation was performed, and the organic layer was washed with 5% brine and dried over anhydrous magnesium sulfate. Concentration under reduced pressure was performed, and the obtained concentrated residue (68.1 g) was subjected to silica gel column chromatography (silica gel 850 g, n-hexane/ethyl acetate = 1/0→20/1→10/1) Purification was performed to obtain ethyl 5-[(1-ethoxy)ethoxy]tetradecanoate (50.6 g) as a colorless oily substance for the purpose. The yield derived from delta-tetradecanolide was 73%.

Example 6: Synthesis of 5-[(1-ethoxy)ethoxy]tetradecanethio acid S-methyl ester

Under a nitrogen atmosphere, add ethyl 5-[(1-ethoxy)ethoxy]tetradecanoate (10.3g, 30.0mmol) and 95% ethanol (38.0g) obtained in the previous step to a 100mL flask And stirred at room temperature. Here, potassium hydroxide (2.0 g, 36.0 mmol) was added and stirred at room temperature for 8 hours. Here, sodium bicarbonate (1.0 g, 12.0 mmol) was added and directly stirred overnight. The reaction solution was concentrated under reduced pressure to obtain a crude yellow solid (10.7 g), so it was directly used in the next step.

In a 200 mL flask, the crude product (10.7 g), ether (107 mL) and triethylamine (0.30 g, 3.0 mmol) obtained in the previous step were added, and the mixture was stirred under ice-water cooling. Here, trimethylacetyl chloride (3.7 mL, 30.0 mmol) was added dropwise over 15 minutes. The solution stirred under ice water cooling for 1 hour was used for the next step.

A 200 mL four-necked flask was charged with 15% methylmercaptan sodium salt aqueous solution (21.0 g, 45.0 mmol), and stirred under ice-water cooling. Here, the total amount of the above reaction solution was added dropwise over 15 minutes, and stirred under ice-water cooling for 30 minutes, and at room temperature for 2 hours. After standing overnight, liquid separation was performed, and the resulting aqueous layer was extracted with ether. The organic layer was mixed, washed with an aqueous sodium bicarbonate solution and saturated brine in this order, and dried over anhydrous sodium sulfate. Concentration under reduced pressure was performed, and the obtained crude product (8.6 g) was subjected to silica gel column chromatography (silica gel 150 g, n-hexane/ethyl acetate = 1/0→50/1→30/1) Refining was carried out to obtain 5-[(1-ethoxy)ethoxy]tetradecanethio acid S-methyl ester (color product of the present invention 2:5.9 g) as a colorless oily substance for the purpose. The yield derived from ethyl 5-[(1-ethoxy)ethoxy]tetradecanoate was 57%.

Physical data of 5-[(1-ethoxy)ethoxy]tetradecane thioacid S-methyl ester

¹ H-NMR (400MHz, CDCl ₃ ): δppm 4.67-4.62 (m, 1H), 3.52-3.38 (m, 3H), 2.43 (t, 1H, J=7.4Hz), 2.34 (t, 1H, J= 7.4Hz), 2.00(s, 3H), 1.89-1.65(m, 2H), 1.60-1.37(m, 5H), 1.29-1.27(m, 16H), 1.16(dt, 3H, J=7.0Hz, 2.1 Hz), 0.93-0.90 (m, 3H)

¹³ C-NMR (100 MHz, CDCl ₃ ): δ ppm 198.35, 198.26, 98.87, 98.72, 75.71, 75.51, 59.83, 59.69, 44.09, 35.12, 34.47, 34.19, 33.48, 32.29, 30.33, 30.30, 30.11, 30.07, 30.03, 29.76,25.82,25.45,23.08,22.01,21.53,20.75,15.68,14.33,11.18

Example 7: Aroma evaluation

For 5-[(1-ethoxy)ethoxy]decane thioacid S-methyl ester (invention product 1), 5-[(1-ethoxy)ethoxy]tetradecanethio Each of the 0.1% ethanol solutions of the acid S-methyl ester (invention product 2) was evaluated for aroma by five trained functional inspectors. Aroma evaluation was performed by preparing the aforementioned 0.1% ethanol solution in a 30 mL sample bottle, using the aroma of the bottle mouth and the odor test paper impregnated with this solution. Table 1 shows the average aroma evaluation of 5 digits.

Example 8: Addition effect of flavoring composition to fresh milk

Each component (mass %) of Table 2 is blended as a fresh milk-like flavor composition. 2.0 g of the present invention product 1 or the present invention product 2 was mixed with the fresh milk blended spice composition (Comparative Product 1) such as Table 2 to prepare a novel fresh milk blended spice composition. The present invention product 3 mixed with the present invention product 1 and the present invention product 4 mixed with the present invention product 2 and the comparative product 1 were subjected to functional evaluation by 10 trained functional inspectors.

As a result, all of the 10 functional inspectors evaluated that the present invention product 3 and the present invention product 4 emphasized good fermented milk feeling and heated milk feeling compared with the comparative product 1.

Example 9: Adding effect to cream-like flavor composition

Each component (mass %) of the blending table 3 is a cream-like flavor composition. To the cream blended flavor composition (Comparative Product 2) such as Table 3, 5.0 g of the present invention product 1 or the present invention product 2 was mixed to prepare a novel cream blended flavor composition. The present invention product 5 mixed with the present invention product 1 and the present invention product 6 and the comparative product 2 mixed with the present invention product 2 were subjected to a functional evaluation by 10 trained functional inspectors.

As a result, all of the ten functional inspectors evaluated that the present invention product 5 and the present invention product 6 emphasized a good creamy feeling and had a thick fat and oily feeling compared with the comparative product 2.

Example 10: Addition effect of hyacinth-like flavor composition

Each component (mass %) of the following Table 4 was blended as a hyacinth-like flavor composition. The hyacinth blended perfume composition (Comparative Product 3) such as Table 4 was mixed with 5.0 g of the inventive product 1 or the inventive product 2 to prepare a novel hyacinth blended perfume composition. The present invention product 7 mixed with the present invention product 1 and the present invention product 8 mixed with the present invention product 2 and the comparative product 3 were subjected to functional evaluation by 10 trained functional inspectors.

As a result, all of the ten functional inspectors evaluated the product 7 of the present invention and the product 8 of the present invention as compared with the comparative product 3, emphasizing the strong aroma of hyacinth.

Example 11: Addition effect of product 1 of the present invention to coffee

According to the coffee blending formula (mass %) of Table 5, coffee was prepared (Control 1).

For 1000 g of coffee (Control 1), after dilution of the present product 1 with ethanol, 10 μg (additional concentration of the present product 1 0.1 ppb: comparative product 4) and 100 μg (additional concentration of the present product 1 1 ppb: the present invention) Product 9), 1 mg (additional concentration of the present invention product 1 10 ppb: the present invention product 10), 10 mg (additional concentration of the present invention product 1 100 ppb: the present invention product 11), 100 mg (additional concentration of the present invention product 1 1 ppm: the present Inventive product 12), 1 g (additive concentration of inventive product 1 10 ppm: inventive product 13), 10 g (additive concentration of inventive product 1 100 ppm: inventive product 14), 100 g (additive concentration of inventive product 1 1000 ppm: Comparative product 5) 1% solution of product 1 of the present invention further diluted with water to prepare coffees of comparative products 4 and 5 and products 9 to 14 of the present invention. Each coffee was flavored by 10 trained functional inspectors. Table 6 shows the comparative evaluation with the control product 1 to which the present invention product 1 is not added.

According to the results in Table 6, the products 9 to 14 of the present invention are given a fresh feeling, and the aroma of coffee is enhanced. In particular, the products 11 and 12 of the present invention are endowed with a good aroma of freshness of coffee, and the aroma of good coffee is emphasized remarkably. On the other hand, the comparative product 4 is not much different from the control product 1, and the comparative product 5 is an evaluation that loses the original aroma of coffee.

Example 12: Addition effect of product 2 of the present invention to coffee

For 1000 g of coffee (Control 1), after dilution of the present product 2 with ethanol, 10 μg (additional concentration of the present product 2 0.1 ppb: Comparative product 6) and 100 μg (additional concentration of the present product 2 1 ppb: the present invention) Product 15), 1 mg (additional concentration of product 2 of the present invention 10 ppb: product 16 of the present invention), 10 mg (additional concentration of product 2 of the present invention 100 ppb: product 17 of the present invention), 100 mg (added concentration of the product 2 of the present invention 1 ppm: the present Inventive product 18), 1 g (additive concentration of inventive product 2: 10 ppm: inventive product 19), 10 g (additive concentration of inventive product 2: 100 ppm: inventive product 20), 100 g (additive concentration of inventive product 2: 1000 ppm: Comparative product 7) 1% solution of the product 2 of the present invention further diluted with water to prepare coffees of the comparative products 6 and 7 and the product of the present invention 15-20. Each coffee was flavored by 10 trained functional inspectors. Table 7 shows the comparative evaluation with the control product 1 to which the present invention product 2 is not added.

According to the results in Table 7, the 15-20 products of the present invention are given a fresh feeling, and the aroma of coffee is enhanced. In particular, the products 17 and 18 of the present invention are endowed with a good aroma of freshness of coffee, and the aroma of good coffee is emphasized remarkably. On the other hand, the comparative product 6 is not much different from the control product 1, and the comparative product 7 is an evaluation for losing the original aroma of coffee.

Example 13: Addition effect of the present invention product 1 to ice cream

According to the ice cream mixing recipe (mass %) of Table 8, ice cream (control 2) was prepared.

For 1000 g of ice cream (Control 2), after dilution of the present product 1 with ethanol, 10 μg (addition concentration of the present product 1 0.1 ppb: Comparative product 8) and 100 μg (addition concentration of the present product 1 1 ppb: the present invention) Product 21), 1 mg (additional concentration of the present product 1 10 ppb: the present product 22), 10 mg (additional concentration of the present product 1 100 ppb: the present product 23), 100 mg (additional concentration of the present product 1 1 ppm: the present Inventive product 24), 1 g (additive concentration of inventive product 1 10 ppm: inventive product 25), 10 g (additive concentration of inventive product 1 100 ppm: inventive product 26), 100 g (additive concentration of inventive product 1 1000 ppm: Comparative product 9) 1% solution of the product 1 of the present invention further diluted with water to prepare ice creams of the comparative products 8 and 9 and the products 21 to 26 of the present invention. The taste of each ice cream was evaluated by 10 trained functional inspectors. Table 9 shows the comparative evaluation with the control product 2 to which the product 1 of the present invention was not added.

According to the results in Table 9, the products 21 to 26 of the present invention were given a fat feeling, and the aroma of fresh milk was enhanced. In particular, the products 23 and 24 of the present invention are imparted with a refreshing fat feeling, and the fresh milk aroma such as good is strongly emphasized. On the other hand, the comparative product 8 is not much different from the control product 2, and the comparative product 9 is an evaluation in which a malodor different from the original aroma of ice cream is felt.

Example 14: Addition effect of product 2 of the present invention to ice cream

For 1000 g of ice cream (control product 2), after diluting the present product 2 with ethanol, 10 μg (adding concentration of the present product 2 0.1 ppb: comparative product 10) and 100 μg (adding concentration of the present product 2 1 ppb: the present invention) Product 27), 1 mg (additional concentration of the present invention product 2 10 ppb: the present invention product 28), 10 mg (additional concentration of the present invention product 2 100 ppb: the present invention product 29), 100 mg (additional concentration of the present invention product 2 1 ppm: the present Inventive product 30), 1 g (additive concentration of inventive product 2: 10 ppm: inventive product 31), 10 g (additive concentration of inventive product 2: 100 ppm: inventive product 32), 100 g (additive concentration of inventive product 2: 1000 ppm: Comparative product 11) A 1% solution of product 2 of the present invention further diluted with water was prepared as ice cream of comparative products 10 and 11, and product 27 to 32 of the present invention. Each ice cream was flavored by 10 trained functional inspectors. Table 10 shows the comparative evaluation with the control product 2 to which the present invention product 2 is not added.

According to the results in Table 10, the products 27 to 32 of the present invention are imparted with a fatty feeling, and the aroma of fresh milk is enhanced. In particular, the products 29 and 30 of the present invention are imparted with a refreshing fat feeling, and the fresh milk aroma such as good is strongly emphasized. On the other hand, the comparative product 10 is not much different from the control product 2, and the comparative product 11 is an evaluation in which a malodor different from the original flavor of ice cream is felt.

Example 15: Addition effect of fresh milk-like flavoring composition on milk tea

The fresh milk blended flavor composition (Comparative Product 1, Inventive Product 3, and Inventive Product 4) obtained in Example 8 was added to the milk tea prepared according to the formula in Table 11, and the milk tea beverage was prepared by the usual method. The milk tea to which the comparative product 1, the present invention product 3, and the present invention product 4 are added is defined as the comparative product 12, the present invention product 33, and the present invention product 34, respectively. The milk tea was evaluated by 20 trained functional inspectors.

As a result, all of the 20 functional inspectors evaluated that the present invention product 33 and the present invention product 34 had a good fat feeling and a thick feeling compared with the comparative product 12, which was good.

Example 16: Adding effect of cream-like flavoring composition on biscuits

The cream-like flavor composition (Comparative Product 2, Inventive Product 5 and Inventive Product 6) obtained in Example 9 was added to the cookie dough prepared according to the formula in Table 12, and baked at 220°C for 7 minutes to prepare Cookies. The biscuits added with the comparative product 2, the present invention product 5 and the present invention product 6 are designated as the comparative product 13, the present invention product 35 and the present invention product 36, respectively. The biscuits were evaluated by 20 trained functional inspectors.

As a result, all of the 20 functional inspectors evaluated that the present invention product 35 and the present invention product 36, compared with the comparative product 13, imparted a unique dense fat feeling and emphasized the thick feeling of cream.

Example 17: Addition effect of hyacinth-like flavor composition to liquid detergent for kitchen

The hyacinth blended perfume composition (Comparative Product 3, Inventive Product 7 and Inventive Product 8) obtained in Example 10 was added to the kitchen liquid detergent prepared according to the formula in Table 13 and prepared by the usual method Liquid detergent for kitchen. The liquid detergent for the kitchen to which the comparative product 3, the present invention product 7 and the present invention product 8 are added is designated as the comparative product 14, the present invention product 37 and the present invention product 38, respectively. These kitchen liquid cleaners were subjected to functional evaluation by 20 trained functional inspectors.

As a result, all of the 20 functional inspectors evaluated that the present invention product 37 and the present invention product 38 gave a hyacinth-like aroma compared to the comparative product 14, and emphasized the richness of the hyacinth.

Claims (7)

A 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester, which is represented by the following formula (1);

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group]. A fragrance composition containing 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the following formula (1) as an active ingredient;

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group]. A composition comprising 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester represented by the following formula (1) and a diluent;

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group]. A fragrant cosmetic or food or drink, which contains 5-[(1-alkoxy)ethoxy]alkylthio acid S-alkyl ester as in claim 1. A fragrant cosmetic or food or drink, which contains the composition as in claim 2 or 3. A 5-[(1-alkoxy)ethoxy]alkyl thioacid S-alkyl ester, which is represented by the following formula (1), and is used to impart fragrance or scent to a cosmetic or food and beverage product;

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group]. A method for imparting or enhancing the fragrance or fragrance of a fragrance or food or drink, which comprises adding an effective amount of the following formula (1) shown in the following formula (1) to a fragrance or cosmetic which needs to impart or enhance fragrance or fragrance -[(1-alkoxy)ethoxy] alkylthio acid S-alkyl ester step;

[In formula (1), R ₁ represents an alkyl group having 1 to 9 carbon atoms, R ₂ represents an alkyl group having 2 to 4 carbon atoms, and R ₃ represents a methyl group or an ethyl group].